Vat dyes and process of making same.



UNITED STATES PATENT rmrzsmenn, on OFFENBACH-ON-THE-MAIN, GERMANY, AssIeNoa'ro CORPORATION on CHEMISCHE FABRIK enrnsnnm-nnnxrnon, or FRANKFORT-ON-THE-MAIN,

Patented Aug. 12,1913.

GERMANY.

VAT DYES AND PROCESS OF MAKING SAME.

1,070,196, Specification of Letters Patent. No Drawing.

Application filed March 30, 1912. Serial No. 687,461.

To all whom it may concern:

Be it known that I, Fnrrz SINGER, doctor 7 of philosophy, chemist, a subject of the Ger man Emperor, and resident of Offenbachon-the-Main, in the Grand Duchy of Hesse, German with postoflice address Mainstrasse, o. 179, have invented new and useful Improvements in Vat Dyes and Processes of Making Same, of which the following is a specification. My invention relates to the manufacture and production of new .vat dyestulfs of'the anthraquinone series which can ,be obtained by acting of diazo. compounds of the aromatic series upon such aromatic amins as contain in the aromatic residue, in which is present the amino group, such substituents, as prevent the entrance of the diazo group in the paraanc'l ortho position to-the amino oup, wherein at least one of these bodies elongs to the anthraquinone series.

The new compounds have probably the following general formula:

wherein R and R means aromatic radicals,

of which one at least belongs to the anthraquinone series. R, may be H, CH 'C H 'COL The reaction is carried out by tombining the diazo com ounds of the anthraquinone Series with amins of the benzene-, na hthalene-, anthracene series and other b0 ice, as contain in the aromatic residue, in which is present the amino group, such substituents, as revent the entrance of the diazo group in t e paraand ortho osition to the amino group, or by acting with diazo compounds. of the benzene, naphthaleneor anthracene series u on amino-anthraquinone.

As su titutes, which prevent the entrance of the diazo group in the para-position wthe amino group, any substitute may be taken, which has its place already in the para-position to the amino group, or negative substitutes, for example halogen or nitro groups, which are in the orthoor metacally I can position to the amino group. The such obfastness against alkaline means of re uction and the leuco compounds thereof can be fixed on the unmordanted fiber and give yellow to red shades by the subsequent oxida- In carrying out the new process practiproceed as follows, parts being by weight;

Example I 23 parts of l-aminoanthraquinone are dissolved in 120 parts of sulfuric acidof 66 B. To this solution ofl-aminoanthraquinone sulfate, cooled with 100 parts .of ice at 10 0., is added a concentrated solution of 8\ parts .of sodium nitrite while stirring until the diazotation is completed, Then water is added until no more dlazoniums'ulfate is recipitated, filtered OE and the residuedisso ved in 2.5 liters of water. Into this solution are ured 10 parts of paratoluidin, dissolve in 10 parts of hydrochloric acid of 20 -B. and 500 parts of water. The formation of dyestuif is completed by addition er sodium acetate. The

precipitated red flakes are filtered, washed and ground with water to a aste. In. dry" shape the dyestutf forms a re powder soluble in nitrobenzene with brown oran e color,

in concentrated sulfuric acid with re orange color. From brown-violet vat cotton is dyed.

orange red shades which on subsequent treatment with a hot soa solution are. turned into yellowish-red 0 very good fastness against'washing and chlorin.

The product obtained by Example I 1s replresented by the following structural formu 0.:

Example II: 25v parts of Q-diaZo-anthraquinone-sulfate dried at low temperature are suspended into 300 parts of concentrated acetic acid. Then 10 parts of 1.5-diamino- In dry state it forms a brown powder'soluble in nitrobenzene with deep orange color, in concentrated sulfuric acid with red orange color. From black-brown vat cotton is dyed orange-brown shades.

The product obtained by Example II is represented by the following structural forwashed with water and ground to a paste. Inula:

Example III: 32 parts of 2.5-dichloranilin are dissolved in 750 parts of concentrated acetic acid and 40 parts of hydrochloric acid of 20 B. and are diazotized with 12 parts of sodium-nitrite. Then 45 parts of finely divided Q-aminoanthraquinone and 50 parts of sodium acetate are added while stirrin well at 3040 0., until the formation 0 the dyestufi is completed. Then the dyestufl is filtered, washed with concentrated acetic acid and water and the residue is ground with water to a paste. The dyestuff forms in dry shape a yellow powder soluble in nitrobenzene with yellow-orange color, in concentrated sulfuric acid with orange red color. From red brown vat cotton is, dyed golden yellow shades.

The product obtained by Example III is represented by the following structural formula:

Some of the dyestufi's obtainable according to the present process are described in the following table:

Color of D estutf obtained y Andthe vat. Dyes cotton.

2-Diazoanthraquip-Toluidin Brown vi- Golden yelolet. low. 8.4-Dichloroanilin ....do Yellow. m-Chloroanilin (orinth Yellow red. Dehydrothiotolu- B l v. c k Orange.

idm. brown 2.5-Dichloroanilin Corinth Yellow red.

Do pChloroanilinn" Bordeaux Orange red.

2-molecules of 2- 1.5-Diam1noan- B l a c k 0 r a n g c diazoanthraqui thraquinone. brown. brown. none.

Do lA'Diaminoan- Reddisli Gray.

thraquinone. d e e p brown. 2-Diazonnthraquip-Aminoacemni- B r o w :1 Orange red.

none. lid. blue. l-Diazoanthrnquip-Toluidin B r o w n Red.

none. violet.

Do pChl0roanilin.... Yellowish- Yellow orbrown ange. blue Do 2.5-Dichloroanilin B :10 w n Yellow red.

ue. 2.5-Dicl1lorodiazo- 2-Aminoauthra- Red brown Golden yelbenzene. quinone. low.

Now What I claim and desire to secure by Letters Patent is the following:

1. The process for the production of vat dyes of the anthraquinone series consisting in combining diazo compounds of the aromatic series with such aromatic amins as contain in the aromatic residue, in which is present the amino group, such substituents, as prevent the entrance of the diazo group in the para and ortho position to the amino group, wherein at least one of these bodies belongs to the anthraquinone series.

2. As new articles, the vat dyes of the anthraquinone series which can be obtained by combining aromatic diazo compounds with such aromatic amins as contain in the aromatic residue, in which is present the amino group, such substituents, as prevent the entrance of the diazo group inthe paraand ortho-position to the amino group, wherein at least one of these bodies belongs to the anthraquinone series, which dyestuffs form brown to yellowish red powders insoluble in water, soluble in nitrobenzene with orange brown to deep orange color, in concentrated sulfuric acid with brown to orange red color and yield with alkaline hydrosulfite a brown Violet to red brown vat, from which cotton is dyed very fast yellow to red shades.

In testimony, that I claim the foregoing as my invention, I have signed my name in presence of two witnesses, this sixteenth day of March 1912,

FRITZ SINGER.

Witnesses PETER LAUTENS HLAGER, Fnrrz Diison. 

